Economical routes to size-specific assembly of self-closing structures

Abstract: Self-assembly is one of the prevalent strategies used by living systems to fabricate ensembles of precision nanometer-scale structures and devices. The push for analogous approaches to create synthetic nanomaterials has led to the development of a large class of programmable crystalline structures. However, many applications require `self-limiting' assemblies, which autonomously terminate growth at a well-defined size and geometry. For example, curved architectures such as tubules, vesicles, or capsids can be designed to self-close at a particular size, symmetry, and topology. But developing synthetic strategies for self-closing assembly has been challenging, in part because such structures are prone to polymorphism that arises from thermal fluctuations of their local curvature, a problem that worsens with increased target size. Here we demonstrate a strategy to eliminate this source of polymorphism in self-closing assembly of tubules by increasing the assembly complexity. In the limit of single-component assembly, we find that thermal fluctuations allow the system to assemble nearby, off-target structures with varying widths, helicities, and chirality. By increasing the number of distinct components, we reduce the density of off-target states, thereby increasing the selectivity of a user-specified target structure to nearly 100%. We further show that by reducing the design constraints by targeting either the pitch or the width of tubules, fewer components are needed to reach complete selectivity. Combining experiments with theory, our results reveal an economical limit, which determines the minimum number of components that are required to create arbitrary assembly sizes with full selectivity. In the future, this approach could be extended to more complex self-limited structures, such as shells or triply periodic surfaces.